TWI610131B - Photosensitive resin composition and color filter using the same - Google Patents

Abstract

A photosensitive resin composition includes (A) a coloring agent including a copolymer represented by Chemical Formula 1 and a green pigment; (B) a binder resin; (C) a photopolymerizable monomer; (D) a photopolymerization initiator; And (E) a solvent, wherein a content of the copolymer represented by Chemical Formula 1 is about 100 parts by weight to about 300 parts by weight based on 100 parts by weight of a green pigment, and a color filter manufactured using the same is provided. [Chemical Formula 1] In Chemical Formula 1, a, b, and c are the same as defined in the detailed description.

Description

Photosensitive resin composition and color filter using the same

This application claims the priority and rights of Korean Patent Application No. 10-2014-0128421 filed in the Korean Intellectual Property Office on September 25, 2014, the entire contents of which are incorporated herein by reference.

The present invention relates to a photosensitive resin composition and a color filter using the same.

Color filters are used in liquid crystal displays (LCDs) and optical filters for cameras. They are thin-film optical components that extract more than 3 colors from white light and act on fine pixel units. Pixels have a size of tens to hundreds of microns. This color filter has a structure in which a black matrix layer is laminated with a predetermined pattern to block a boundary between a pixel and a pixel region including red (R), green (g), and blue The three primary colors of (B) are sequentially arranged on a transparent substrate in a predetermined order.

Generally, a color filter can be constructed by dyeing, electrophoretic deposition, printing, pigment dispersion coating three or more colors on a transparent substrate, and recently, a pigment dispersion using a pigment-dispersible color resist has been mainly used. .

A pigment dispersion method forms a colored film by repeating a series of processes such as coating, exposing, developing, and curing a photopolymerizable composition containing a colorant on a transparent substrate containing a black matrix. The pigment dispersion method can improve heat resistance and durability, which are extremely important features of a color filter, and can provide a film having a uniform thickness. Therefore, the method is widely used.

Recently, large liquid crystal displays (LCDs) require high brightness and high contrast ratios, but to meet these requirements, color reproducibility of color filters may be reduced.

One embodiment provides a photosensitive resin composition having excellent heat resistance and chemical resistance, as well as dispersion stability and coloring characteristics.

Another embodiment provides a color filter having excellent color reproducibility and high brightness and high contrast ratio by using a photosensitive resin composition.

在化學式1中， a是在1到100範圍內的整數，b是在1到100範圍內的整數，並且c是在1到50範圍內的整數。One embodiment provides a photosensitive resin composition including (A) a coloring agent including a copolymer represented by Chemical Formula 1 and a green pigment; (B) a binder resin; (C) a photopolymerizable monomer; (D) ) A photopolymerization initiator; and (E) a solvent, wherein the content of the copolymer represented by Chemical Formula 1 is about 100 parts by weight to about 300 parts by weight based on 100 parts by weight of the green pigment. [Chemical Formula 1]

In Chemical Formula 1, a is an integer in the range of 1 to 100, b is an integer in the range of 1 to 100, and c is an integer in the range of 1 to 50.

The content of the copolymer represented by Chemical Formula 1 may be about 100 parts by weight to about 250 parts by weight based on 100 parts by weight of the green pigment.

The copolymer represented by Chemical Formula 1 may be a yellow dye.

The copolymer represented by Chemical Formula 1 may have a maximum absorption wavelength in a wavelength region of about 460 nm to about 560 nm, and a transmittance of about 80% to about 100% in a wavelength region of about 560 nm to about 660 nm.

The copolymer represented by Chemical Formula 1 may have a thermal decomposition temperature of about 250 ° C to about 500 ° C.

The copolymer represented by Chemical Formula 1 may have a weight average molecular weight of about 3,000 g / mole to about 50,000 g / mole.

The copolymer represented by Chemical Formula 1 may have an acid value of about 20 mg KOH / g to about 200 mg KOH / g.

The green pigment may include at least one selected from C.I. green pigment 7, C.I. green pigment 36, and C.I. green pigment 58.

The colorant may further include a yellow pigment, a red pigment, or a combination thereof.

The yellow pigment may include at least one selected from CI yellow pigment 138, CI yellow pigment 139, CI yellow pigment 150, and CI yellow pigment 185, and the red pigment may include at least one selected from CI red pigment 177 and CI red pigment 254 .

The photosensitive resin composition may include about 2% to about 12% by weight of a coloring agent (A); about 1% to about 10% by weight of a binder resin (B); and about 2% to about 20% by weight Photopolymerizable monomer (C); about 0.1% to about 4% by weight of a photopolymerization initiator (D); and the balance of a solvent (E).

The photosensitive resin composition may include at least one additive selected from the group consisting of malonic acid, 3-amino-1,2-propanediol, a coupling agent having a vinyl group or a (meth) acrylic acid group, a leveling agent, and a fluorine compound. Surfactants; and free radical polymerization initiators.

Another embodiment provides a color filter manufactured using the photosensitive resin composition.

The color filter may have a value greater than or equal to about 35%, such as greater than or equal to about 68%, such as greater than or equal to about 72%, such as greater than or equal to about 80%, such as greater than or equal to, relative to NTSC (CIExy 1931 color coordinates). About 85% color reproducibility.

Other embodiments are included in the following specific implementations.

A color filter having excellent color reproducibility, high brightness, and high contrast ratio can be achieved by using a photosensitive resin composition having excellent high brightness and high contrast ratio, as well as excellent dispersion stability and coloring characteristics.

Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are merely exemplary, and the present invention is not limited thereto.

As used herein, when a specific definition is not otherwise provided, the term "substituted" refers to substitution with at least one substituent selected from the group consisting of a halogen atom (F, Cl, Br or I), a hydroxyl group , C1 to C20 alkoxy, nitro, cyano, amino, imino, azide, methylamidino, hydrazino, hydrazino, carbonyl, carbamoyl, thiol, ester, ether , Carboxyl or its salt, sulfonic acid or its salt, phosphoric acid or its salt, C1 to C20 alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C3 to C20 cycloalkyl, C3 To C20 cycloalkenyl, C3 to C20 cycloalkynyl, C2 to C20 heterocycloalkyl, C2 to C20 heterocycloalkenyl, C2 to C20 heterocycloalkynyl, C3 to C30 heteroaryl, or a combination thereof.

As used herein, when a specific definition is not otherwise provided, the term "hetero" may refer to a substitution with at least one N, O, S, and P heteroatom in place of at least one C in a cyclic substituent.

As used herein, when a specific definition is not otherwise provided, "(meth) acrylate" refers to both "methacrylate" and "methacrylate", and "(meth) acrylate" refers to "methacrylic acid" "And methacrylic acid."

As used herein, when a specific definition is not otherwise provided, the term "combination" refers to mixing or copolymerization.

As used herein, unless a specific definition is provided otherwise, when a chemical bond is not drawn, a hydrogen atom is bonded at a location presumably given.

As used herein, when a specific definition is not otherwise provided, "*" indicates a point where the same or different atom or chemical formula is connected.

在化學式1中， a是在1到100範圍內的整數，b是在1到100範圍內的整數，並且c是在1到50範圍內的整數。A photosensitive resin composition according to one embodiment includes: (A) a coloring agent including a copolymer represented by Chemical Formula 1 and a green pigment; (B) a binder resin; (C) a photopolymerizable monomer; (D) light A polymerization initiator; and (E) a solvent, wherein the content of the copolymer represented by Chemical Formula 1 is about 100 to about 300 parts by weight based on 100 parts by weight of the green pigment. [Chemical Formula 1]

In Chemical Formula 1, a is an integer in the range of 1 to 100, b is an integer in the range of 1 to 100, and c is an integer in the range of 1 to 50.

The copolymer represented by Chemical Formula 1 has improved solubility in an organic solvent, and does not have particles in a solution or particles having an initial particle diameter of several nanometers or less, unlike pigments or pigment derivative particles. That is, the copolymer represented by Chemical Formula 1 can be used as a dye without particles, and thus light scattering is reduced and a high contrast ratio can be achieved.

In addition, when the color filter has high color reproducibility with respect to NTSC (CIExy 1931 color coordinate) of greater than or equal to about 35%, such as greater than or equal to about 68%, such as greater than or equal to about 72%, the amount of pigment is generally The pattern characteristics of the photosensitive resin composition are increased and thus decreased, and the light emission characteristics may be reduced. However, because the copolymer represented by Chemical Formula 1 functions as a yellow coloring compound, that is, a yellow dye, it can replace a conventional yellow pigment or can be mixed with a conventional yellow pigment and reduce the amount of the yellow pigment and thus can achieve high light emitting characteristics and high Color reproducibility. In addition, the copolymer represented by Chemical Formula 1 has more improved coloring characteristics than a conventional yellow pigment.

In general, monomer dyes may move to the surface of the film due to increased mobility during heating of the photosensitive resin composition, or may be eluted by another chemical solution during the manufacturing process. According to one embodiment, since the copolymer represented by Chemical Formula 1 which can be used as a dye (for example, a yellow dye) is a polymer, it can be crosslinked with a monomer in the photosensitive resin composition, and the dye can be reduced by a crosslinking bond. And increase film hardness, and therefore reduce the elution of copolymer dyes even if other chemical solution intrusions occur during the manufacturing process.

Hereinafter, each component is described in detail. ( A ) Colorant

The photosensitive resin composition according to one embodiment includes a colorant including a copolymer represented by Chemical Formula 1 and a green pigment.

The content of the copolymer represented by Chemical Formula 1 is about 100 parts by weight to about 300 parts by weight, for example, about 100 parts by weight to about 250 parts by weight, based on 100 parts by weight of the green pigment. When the copolymer represented by Chemical Formula 1 is included in the range, the coloring characteristics and transmittance are improved.

The copolymer represented by Chemical Formula 1 is a yellow colored compound such as a yellow dye. When the copolymer represented by Chemical Formula 1 is added to the photosensitive resin composition, the amount of the pigment is reduced and thus dispersion stability and coloring characteristics can be improved.

The copolymer represented by Chemical Formula 1 has high durability due to the improved solubility in an organic solvent as described above. In addition, the copolymer represented by Chemical Formula 1 can be used as a yellow dye, and thus a dispersion liquid of a pigment can be easily prepared and the amount of the yellow pigment can be reduced. Therefore, when the copolymer represented by Chemical Formula 1 is used to prepare a photosensitive resin composition, a color filter having high brightness and high contrast ratio in a desired color coordinate can be realized.

In the spectroscopic analysis, the copolymer represented by Chemical Formula 1 may have a maximum absorption wavelength in a wavelength region of about 460 nm to about 560 nm, and may have about 80% to about 560 nm to about 660 nm. Approximately 100% transmittance. Herein, the solvent may be propylene glycol monomethyl ether acetate (PGMEA) and the like. Within the range of spectral characteristics, high brightness can be achieved.

The copolymer represented by Chemical Formula 1 may have high heat resistance. Specifically, the copolymer represented by Chemical Formula 1 may have a thermal decomposition temperature greater than or equal to about 250 ° C, for example, about 250 ° C to about 500 ° C.

The copolymer represented by Chemical Formula 1 may have a weight average molecular weight of about 3,000 g / mole to about 50,000 g / mole, for example, about 5,000 g / mole to about 20,000 g / mole. The copolymer represented by Chemical Formula 1 may have an acid value of about 20 mg KOH / g to about 200 mg KOH / g, for example, about 50 mg KOH / g to about 150 mg KOH / g. When the weight average molecular weight and the acid value are within the ranges, dispersion stability and coloring characteristics are improved.

On the other hand, in addition to the copolymer represented by Chemical Formula 1, the colorant further contains a green pigment. The green pigment may include at least one selected from C.I. green pigment 7, C.I. green pigment 36, and C.I. green pigment 58.

In addition to the green pigment, the colorant may further include a yellow pigment, a red pigment, or a combination thereof. The yellow pigment may include at least one selected from CI yellow pigment 138, CI yellow pigment 139, CI yellow pigment 150, and CI yellow pigment 185, and the red pigment may include at least one selected from CI red pigment 177 and CI red pigment 254 . In some embodiments, the photosensitive resin composition may include about 0.5% by weight, 1% by weight, 1.5% by weight, 2% by weight, 2.5% by weight, 3% by weight, 3.5% by weight, 4% by weight, 4.5% by weight, or Pigment in an amount of 5% by weight.

The photosensitive resin composition may further contain a dispersant to improve uniform dispersion of the copolymer represented by Chemical Formula 1 and the green pigment in a solvent.

The dispersant may be a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like. Specific examples of the dispersant may be polyalkylene glycols and their esters, polyoxyalkylenes, polyol ester alkylene oxide addition products, alcohol alkylene oxide addition products, sulfonates, sulfonates, carboxylic acid esters, carboxylic acids Salts, alkylamidoamine alkylene oxide addition products, alkylamines, etc., and they can be used alone or as a mixture of two or more.

Examples of commercially available dispersants may include DISPERBYK-101, DISPERBY-130, DISPERBY-140, DISPERBY, manufactured by BYK Co., Ltd., Germany. D-Spiker-160, D-Spiker-161, D-Spiker-162, D-Spiker-163, D-Spiker-164, D-Spiker-165, D-Spiker-166, D-Spiker -170, Disco-171, Disco-182, Disco-2000, Disco-2001, etc .; Efka made by EFKA Chemicals Co.- 47, Efka-47EA, Efka-48, Efka-49, Efka-100, Efka-400, Efka-450; cables manufactured by Zenka Co. Solsperse 5000, Sospers 12000, Sospers 13240, Sospers 13940, Sospers 17000, Soss 20000, Soss 24000GR, Soss 27000, Soss 28000, etc .; or flavor PB711, PB821, etc. manufactured by Ajinomoto Inc.

The content of the dispersant may be about 0.01% by weight to about 15% by weight based on the total weight of the photosensitive resin composition. When the dispersant is included in the above range, the dispersion of the photosensitive resin composition can be improved by an appropriate viscosity, and thus the optical and physicochemical quality of the article can be maintained.

The pigment may be injected into the photosensitive resin composition as a dispersion containing a mixture of a pigment, a dispersant, and a solvent. The solvent of the pigment dispersion liquid may be ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like.

The content of the colorant may be about 2% to about 12% by weight, for example, about 4% to about 12% by weight based on the total amount of the photosensitive resin composition. When the colorant is included in the range, it can provide excellent color characteristics and can exhibit high brightness and high contrast ratio under the same color coordinates. ( B ) Adhesive resin

The photosensitive resin composition according to one embodiment includes a binder resin, such as an acrylic fluorene-based binder resin.

The propylene fluorene-based resin is a copolymer of a first olefinic unsaturated monomer and a second olefinic unsaturated monomer copolymerizable with the first olefinic unsaturated monomer, and a resin containing at least one propylene fluorene-based repeating unit. .

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and examples of the monomer include (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid Or a combination.

The content of the first ethylenically unsaturated monomer may be in a range of about 5 wt% to about 50 wt%, and specifically about 10 wt% to about 40 wt% based on the total amount of the acryl fluorene-based resin.

The second ethylenically unsaturated monomer may include an aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl methyl ether, and the like; an unsaturated carboxylic acid ester compound such as (methyl (Methyl) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzene (meth) acrylate Methyl ester, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, etc .; unsaturated alkyl carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate, 2-methyl (meth) acrylate Dimethylaminoethyl, etc .; Vinyl carboxylic acid compounds, such as vinyl acetate, vinyl benzoate, etc .; Unsaturated carboxylic acid glycidyl ester compounds, such as glycidyl (meth) acrylate, etc .; Vinyl cyanide compounds, such as (Meth) acrylonitrile and the like; unsaturated fluorenamine compounds such as (meth) acrylamide and the like; and the like. It can be used singly or in a mixture of two or more.

Specific examples of the acrylic fluorene-based resin may be acrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer Polymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, etc. , But not limited to this. It can be used singly or in a mixture of two or more.

The acrylic fluorene-based adhesive resin may have a weight average molecular weight of about 3,000 g / mol to 50,000 g / mol, for example, about 5,000 g / mol to 40,000 g / mol. When the weight average molecular weight of the acrylic fluorene-based adhesive resin is within the range, close contact with the substrate and physicochemical characteristics can be improved, and appropriate viscosity can be provided.

The content of the binder resin may be about 1% to about 10% by weight, for example, about 1% to about 8% by weight based on the total amount of the photosensitive resin composition. When the binder resin is included in the above range, developability can be improved, and excellent surface smoothness can be improved due to improved cross-linking during color filter manufacturing. ( C ) Photopolymerizable monomer

The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid containing at least one ethylenically unsaturated double bond.

The photopolymerizable monomer has an ethylenically unsaturated double bond, and therefore, sufficient polymerization can be caused during exposure during pattern formation and a pattern having excellent heat resistance, light resistance, and chemical resistance can be formed.

Specific examples of the photopolymerizable monomer may be ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (methyl) ) Acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (Meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol mono Methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acryloxyethyl phosphate, phenolic epoxy (meth) acrylate, and the like.

Examples of commercially available reactive unsaturated compounds are as follows. Monofunctional (meth) acrylates can include Aronix M-101 ^® , M-111 ^® , M-114 ^® (Toagosei Chemistry Industry Co., Ltd.); card KAYARAD TC-110S ^® , TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V-2311 ^® (Osaka Organic Chemical Industry Co., Ltd. Organic Chemical Ind., Ltd.)). Examples of bifunctional (meth) acrylates may include Agnex M-210 ^® , M-240 ^® , M-6200 ^® (Toa Synthetic Chemical Industry Co., Ltd.), Kayared HDDA ^® , HX-220 ^® , R-604 ^® (Nippon Kayaku Co., Ltd.), V-260 ^® , V-312 ^® , V-335 HP ^® (Osaka Organic Chemical Industry Co., Ltd.), etc. Examples of trifunctional (meth) acrylates may include Alnacs M-309®, M-400®, M-405®, M-450®, M-7100®, M-8030®, M-8060® ( Toa Synthetic Chemical Industry Co., Ltd.), Kayared TMPTA®, DPCA-20®, DPCA-30®, DPCA-60®, DPCA-120® (Nippon Kayaku Co., Ltd.), V-295®, V-300 ®, V-360®, V-GPT®, V-3PA®, V-400® (Osaka Organic Chemical Industry Co., Ltd.), etc. These substances may be used singly or in a mixture of two or more.

The photopolymerizable monomer may be treated with an acid anhydride to improve developability.

The content of the photopolymerizable monomer may be an amount of about 2% to about 20% by weight, for example, about 3% to about 15% by weight based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included in the range, pattern characteristics and developability can be improved during color filter manufacturing. ( D ) Photopolymerization initiator

The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, an oxime-based compound, and the like.

Examples of the acetophenone-based compound may be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylacetophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (Methylthio) phenyl) -2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -but-1-one, etc. .

Examples of the benzophenone-based compound may be benzophenone, benzophenone benzoate, benzophenone benzoate methyl ester, 4-phenylbenzophenone, hydroxybenzophenone, acrylated diphenyl Ketone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4, 4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of thioxanthone compounds may be thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone , 2-chlorothioxanthone and so on.

Examples of the benzoin-based compound may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Examples of the triazine compound may be 2,4,6-trichloro-s-triazine, 2-phenyl4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4 '-Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) ) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (tri (Chloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthol 1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol 1-yl) -4,6-bis (trichloro (Methyl) -s-triazine, 2--4-bis (trichloromethyl) -6-sunfloweryl-s-triazine, 2--4-bis (trichloromethyl) -6- (4-methoxy Styrenyl) -s-triazine and the like.

Examples of the oxime-based compound may be an O-fluorenyl oxime-based compound, 2- (O-benzylidene oxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1 -(O-acetamoxime) -1- [9-ethyl-6- (2-methylbenzyl) -9H-oxazol-3-yl] ethanone, 0-ethoxycarbonyl-α- Oxyamino-1-phenylpropan-1-one and the like. Examples of the O-fluorenyl oxime may be 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-benzene ) -But-1-one, 1- (4-phenylthiophenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylthiobenzene ) -Octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylthiophenyl) -oct-1-oneoxime-O-acetate, 1- (4-phenylthiophenyl) -butan-1-oneoxime-O-acetate and the like.

The photopolymerization initiator may further include an oxazole-based compound, a dione-based compound, a boric acid fluorene-based compound, a diazonium-based compound, an imidazole-based compound, a biimidazole-based compound, and the like in addition to the compound.

The content of the photopolymerization initiator may be about 0.1% to about 4% by weight, for example, about 0.2% to about 3% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the range, the composition may be sufficiently photopolymerized when exposed during a pattern forming process for preparing a color filter, achieving excellent sensitivity and improving transmittance. ( E ) Solvent

The solvent is a material having compatibility with a coloring agent, a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, but does not react therewith.

The solvent is not particularly limited, but examples of the solvent include alcohols such as methanol, ethanol, and the like; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, tetrahydrofuran, and the like; glycol ethers such as ethyl Glycol methyl ether, ethylene glycol ether, propylene glycol methyl ether, etc .; Cellosolve acetates, such as cellosolve methyl acetate, cellosolve ethyl acetate, cellosolve diethyl acetate, etc .; carbitol, Methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethyl ether Glycol diethyl ether, etc .; propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol propyl ether acetate, etc .; aromatic hydrocarbons, such as toluene, xylene, etc .; ketones, such as methyl ethyl ketone, Cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone, etc .; saturated aliphatic monocarboxylic acids Alkyl esters, such as ethyl acetate, n-butyl acetate, isobutyl acetate, etc .; alkyl lactates, such as methyl lactate, ethyl lactate, etc .; alkyl glycolates, examples Such as methyl glycolate, ethyl glycolate, butyl glycolate, etc .; alkoxyalkyl acetates, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxylate Methyl ester, ethoxyethyl acetate, etc .; alkyl 3-hydroxypropionate, such as methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, etc .; alkyl 3-alkoxypropionate, For example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, etc .; alkyl 2-hydroxypropionate , Such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, etc .; alkyl 2-alkoxypropionate, such as methyl 2-methoxypropionate, 2 -Ethyl methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, etc .; alkyl 2-hydroxy-2-methylpropionate, such as 2-hydroxy-2 -Methyl methylpropionate, ethyl 2-hydroxy-2-methylpropionate, etc .; alkyl 2-alkoxy-2-methylpropionate, such as 2-methoxy-2-methylpropionate Methyl ester, 2-ethoxy-2-methyl propionate, etc .; esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methyl ethyl propionate, hydroxyethyl acetate Hydroxy-3-methylbutyrate and the like; a ketone, or ester compound, such as acetone and ethyl. In addition, the solvent may be N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylarsine, benzyl ether, dihexyl ether, acetone, isophorone, hexanoic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzene acetate Methyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, cellosolve phenyl acetate, and the like. These substances may be used singly or in a mixture of two or more.

In consideration of miscibility, reactivity, etc., the solvent may include glycol ethers, such as ethylene glycol monoethyl ether, etc .; ethylene glycol alkyl ether acetates, such as cellosolve ethyl acetate, etc .; esters, such as propionic acid 2 -Hydroxyethyl, etc .; diethylene glycol, such as diethylene glycol monomethyl ether, etc .; or propylene glycol alkyl ether acetate, such as propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, and the like.

The solvent may be included in a balance based on the total amount of the photosensitive resin composition, and specifically, in an amount ranging from about 20% by weight to about 90% by weight. When the solvent is included in the range, the photosensitive resin composition may have an appropriate viscosity and thus may improve physical and optical characteristics of the article. ( F ) Other additives

The photosensitive resin composition may further include other additives, such as malonic acid; 3-amino-1,2-propanediol; a silane-based coupling agent containing a vinyl or (meth) acryloxy group; a leveling agent; a fluorine-based Surfactants; and radical polymerization initiators to prevent stains or spots during coating, adjust flatness, or prevent pattern residues due to undeveloped.

Additives can be controlled based on the desired characteristics.

The coupling agent may be a silane-based coupling agent, and examples of the silane-based coupling agent may be trimethoxysilylbenzoic acid, γ-methacrylfluorenyloxypropyltrimethoxysilane, vinyltriethoxysilane , Vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, etc. These substances may be used singly or as a mixture of two or more.

The content of the silane-based coupling agent may be about 0.01 to about 1 part by weight based on the total amount of the photosensitive resin composition.

The photosensitive resin composition may further contain a fluorine-based surfactant as needed.

Examples of the fluorine-based surfactant may include, but are not limited to, F-482, F-484, F-478, F-554, and the like manufactured by Dainippon Ink Chemical Industry Co., Ltd. (DIC Co., Ltd.).

The content of the fluorine-based surfactant may be about 0.01% to about 1% by weight, for example, about 0.01% to about 0.8% by weight based on the total amount of the photosensitive resin composition. When the fluorine-based surfactant is included in the range, the composition may generate fewer impurities after development.

The photosensitive resin composition according to one embodiment may be an alkaline developing type capable of being cured by radiating light and developing with an alkaline aqueous solution. When a photosensitive resin composition is laminated on a substrate and irradiated with actinic rays to form a pattern for a color filter, the photosensitive resin composition reacts through actinic rays, and therefore, compared with a non-reactive region The solubility of the reaction zone is drastically reduced, and therefore, only the non-reaction zone can be selectively dissolved. In this way, the solution from which the non-exposed area is removed is called a developing solution, and this developing solution is classified into two types, such as an organic solvent type and an alkaline developing type. Since the organic solvent type developing solution causes air pollution and causes damage to the human body, an alkaline developing type solution may be used as far as the environment is concerned. The photosensitive resin composition according to one embodiment uses an alkaline developing type solution, and therefore, it can be effectively used in terms of environment.

According to another embodiment of the present invention, a color filter manufactured using a photosensitive resin composition is provided.

This color filter can be used in a general method, but to be precise, a photosensitive resin composition is spin-coated, roll-coated, slit-coated, or the like on glass to have a thickness in a range of about 3.0 to about 4.0 microns. Manufacturing method. After coating, ultraviolet (UV) rays are radiated to form the pattern required for the color filter. The coating layer is treated with an alkaline developing solution, and the unirradiated area can be dissolved to form a pattern for the image color filter. . Depending on the required number of R, G, and B colors, this process is repeated to produce a color filter having a desired pattern. In addition, image patterns obtained by curing and development such as heat treatment, actinic ray radiation, and the like improve crack resistance, solvent resistance, and the like.

The color filter using the photosensitive resin composition has high brightness and high contrast ratio.

The color filter using the photosensitive resin composition may have a ratio of about 35% or more with respect to NTSC (CIExy 1931 color coordinate), such as about 68% or more, such as about 72% or more, such as about 72% or more Color reproducibility of 80%, such as greater than or equal to about 85%.

Hereinafter, the present invention is described in more detail with reference to examples. However, these examples should not be construed as limiting the scope of the invention in any sense. (Preparation of copolymer) Preparation Example 1 : Preparation of monomer

As shown in the following reaction scheme 1, a monomer (chemical formula 12) is synthesized. [Reaction Scheme 1]

56.56 g (0.5 mole) of compound (1) and 52.57 g (0.5 mole) of compound (2) were mixed and reacted at 70 ° C for 3 hours to obtain compound (3). Compound (3) was cooled to room temperature, and 150 ml of ethanol and 69.67 g (0.6 mol) of compound (4) were added and heated at 45 ° C. Then, 220 ml (3 mole concentration) of potassium hydroxide in ethanol solution was added dropwise and the resulting mixture was reacted at 80 ° C for 7 hours. The solvent was removed from the obtained reaction, 55 g of sodium chloride (NaCl) was added and filtered and the precipitate was removed. The reaction was dried using magnesium sulfate (MgSO ₄ ), and the solvent was removed to obtain 114.80 g of compound (5), and the yield was 96.4%.

26.33 g (0.36 mole) of compound (6), 66.49 g (0.3 mole) of compound (7) and 150 ml of o-dichlorobenzene were mixed and heated at 60 ° C. 15 ml of a 10 mol sodium carbonate aqueous solution was added dropwise to the obtained reaction solution and the mixture was stirred for 30 minutes. After the mixture was stirred for 2 hours, the mixture was cooled to room temperature, and filtered and washed with water to obtain 73.2 g of compound (8) in a yield of 94.5%.

30.2 g of reduced iron, 22.0 g of acetic acid, and 63.0 g of water were mixed and stirred at 80 ° C., and then 25.83 g of the compound (8) was gradually added to the resulting mixture, and 100.0 ml of ethanol was added dropwise thereto. Subsequently, the resulting mixture was stirred at 80 ° C for 1 hour. The mixture was cooled to room temperature, 26.0 g of sodium carbonate was added thereto, 200 ml of methanol was added and the mixture was stirred for 30 minutes. The resulting mixture was filtered using a celite filter and rinsed with acetone to remove the solvent in the liquid phase. The obtained reaction solution was dissolved in 500 ml of acetone, and insoluble matter was removed. The obtained reaction solution was dried using sodium sulfate and then concentrated to obtain 18.2 g of compound (9) with a yield of 79%.

11.42 g of compound (9), 48 ml of 36% hydrochloric acid, and 210 ml of distilled water were mixed, and the resulting mixture was cooled to 0 ° C. While the internal temperature was maintained at 5 ° C or lower, an aqueous sodium nitrite solution (3.35 g of NaNO ₂ and 40 g of water) was added dropwise to the mixture. After the dropwise addition, the mixed solution was stirred for 3 hours to obtain a compound (10) while maintaining the temperature at 5 ° C to 10 ° C.

Mix 14.3 g of compound (5) and 90 g of water, and add a solution containing 2 equivalents of an aqueous sodium hydroxide solution to prepare a separate solution, thereby adjusting the pH to 8, and slowly drop the compound (10 at 0 ° C) ). A 10% sodium carbonate aqueous solution was added dropwise to the reaction solution to adjust the pH to 6 to 7. The resulting mixture was filtered, 500 ml of acetone was dissolved, activated carbon and sodium sulfate were added, and the resultant was then filtered using a celite filter. Subsequently, the solvent was removed from the solution, and the obtained solid was dried under vacuum to obtain 14.10 g of compound (11) with a yield of 58.8%.

6.07 g of triethylamine, 2.93 g of N, N-dimethylaminopyridine, 6.17 g of methacrylic anhydride and 9.59 g of compound (11) dissolved in 100 ml of acetonitrile were reacted at room temperature for 6 hours, and the excess was poured into Water was distilled to form a precipitate, and the resulting precipitate was filtered, washed with distilled water, and dried to obtain 9.88 g of compound (12) in a yield of 90.2%. Preparation Example 2 : Preparation of copolymer

在化學式1-1中，a=19，b=19，並且c=9。（製備感光性樹脂組合物） 實例 1 到實例 3 以及比較實例 1 到比較實例 5 1,000 grams of cyclohexanone (Shiny Chemical Industrial Co., Ltd.) was heated to 80 ° C in a 10-liter polymerization reactor equipped with a reflux cooler and a stirrer, and slowly added by dissolution 300 g of compound (12), 300 g of benzyl methacrylate (Hitach Ltd.), 106 g of methacrylic acid (Daejung Chemicals & Metals Co., Ltd.), and 92 grams of a solution of 2,2'-azobisisobutyronitrile (Wako Chemicals, Inc.) in 5000 grams of cyclohexanone (Tengyi Chemical Co., Ltd.) to the heated polymerization reaction Device, which lasted 3 hours. When the addition was completed, the mixture was stirred for 14 hours to obtain a polymer containing a repeating unit represented by Chemical Formula 1-1. The polymer had a weight average molecular weight of 9,800 g / mol and an acid value of 100 mg KOH / g when measured by using gel permeation chromatography (GPC) manufactured by Waters Co. [Chemical Formula 1-1]

In Chemical Formula 1-1, a = 19, b = 19, and c = 9. (Preparation of photosensitive resin composition) Examples 1 to 3 and Comparative Examples 1 to 5

評估 ∶ 色彩特徵 The photopolymerization initiator was dissolved in a solvent, the composition is provided in Table 1 below, and the solution was stirred at room temperature for 1 hour. Then, a binder resin having a composition of Table 1 and a photopolymerizable monomer were added thereto, and the resulting mixture was stirred at room temperature for 1 hour. A fluorine-based surfactant having the composition of Table 1 was added thereto, and the resulting mixture was stirred at room temperature for 1 hour. After adding a coloring agent having the composition of Table 1 and stirring the resulting mixture at room temperature for 2 hours, the solution was filtered three times to remove impurities, and the photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 were prepared. . The components used for the photosensitive resin composition are as follows. (A) Colorant (A-1) Copolymer of Production Example 2 (A-2) CI yellow pigment 150 (A-3) CI green pigment 58 (A-4) CI green pigment 36 (A-5) CI green Pigment 7 (B) Adhesive resin polyphenyl methacrylate resin (NPR1520, Miwon Commercial Co., Ltd. (C) Photopolymerizable monomer dipentaerythritol hexaacrylate (DPHA, Japan Chemical Pharmaceutical Co., Ltd.) (D) Photopolymerization initiator oxime (CGI-124, BASF) (E) Solvent propylene glycol methyl ethyl acetate (Sigma-aldrich) (F) Fluorosurfactant F-554 (Dai Nihon Ink Chemical Industry Co., Ltd.) (Table 1) (Unit:% by weight)

Evaluation : color characteristics

The photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 5 were applied to 3.0 μm to 4.0 μm, respectively, and dried on a hot plate at 90 ° C. for 1 minute to obtain each film. After irradiating the resulting film with an exposure dose of 100 mJ / cm2 (365 nm reference) and baking the film in an oven at 230 ° C for 30 minutes, it was measured using an MCPD3000 spectrophotometer from Otsuka Electronics Co., Ltd. Brightness, contrast ratio, heat resistance, chemical resistance, and color reproducibility, and the results are shown in Table 2 below. (Table 2)

From Table 2, the photosensitive resin composition including the copolymer according to Preparation Example 2 exhibited higher brightness as the amount of the yellow pigment was reduced compared to the composition according to Comparative Example 1 to Comparative Example 3 without a copolymer. And contrast ratio. A photosensitive resin combination including the copolymer according to Preparation Example 2 from 100 parts by weight to 300 parts by weight based on 100 parts by weight of a green pigment compared to the composition outside the amount range according to Comparative Examples 4 and 5 Objects show improved lightness and contrast.

Although the present invention has been described in connection with what is presently considered to be a practical exemplary embodiment, it should be understood that the invention is not limited to the disclosed embodiments, but rather the present invention is intended to cover the spirit and scope of the scope of patents included in the attached application Various modifications and equivalent arrangements within. Therefore, the above-mentioned embodiments should be understood as exemplary but not limiting the present invention in any way.

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Claims (12)

A photosensitive resin composition comprising: a coloring agent comprising a copolymer represented by Chemical Formula 1 and a green pigment; a binder resin; a photopolymerizable monomer; a photopolymerization initiator; and a solvent, wherein The content of the copolymer is 100 to 300 parts by weight based on 100 parts by weight of the green pigment:

Where in Chemical Formula 1, a is an integer in the range of 1 to 100, b is an integer in the range of 1 to 100, c is an integer in the range of 1 to 50, and * indicates where the same or different atom or chemical formula is connected Point, wherein the photosensitive resin composition includes 2 to 12% by weight of the colorant; 1 to 10% by weight of the binder resin; and 2 to 20% by weight of the light Polymerizable monomer; 0.1 to 4% by weight of the photopolymerization initiator; and a balance of the solvent. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the content of the copolymer represented by Chemical Formula 1 is from 100 parts by weight to 250 parts by weight based on 100 parts by weight of the green pigment. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the copolymer represented by Chemical Formula 1 is a yellow dye. The photosensitive resin composition according to item 1 of the patent application range, wherein the copolymer represented by Chemical Formula 1 has a maximum absorption wavelength in a wavelength region of 460 nm to 560 nm, and a wavelength of 560 nm to 660 nm. 80% to 100% transmission in the wavelength region. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the copolymer represented by Chemical Formula 1 has a thermal decomposition temperature of 250 ° C to 500 ° C. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the copolymer represented by Chemical Formula 1 has a weight average molecular weight of 3,000 g / mole to 50,000 g / mole. The photosensitive resin composition according to item 1 of the patent application range, wherein the copolymer represented by Chemical Formula 1 has an acid value of 20 mg KOH / g to 200 mg KOH / g. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the green pigment includes at least one selected from the group consisting of C.I. green pigment 7, C.I. green pigment 36, and C.I. green pigment 58. The photosensitive resin composition according to item 1 of the scope of patent application, wherein The colorant further includes a yellow pigment, a red pigment, or a combination thereof. The photosensitive resin composition according to item 9 of the scope of patent application, wherein the yellow pigment includes at least one selected from CI yellow pigment 138, CI yellow pigment 139, CI yellow pigment 150, and CI yellow pigment 185, and The red pigment includes at least one selected from CI red pigment 177 and CI red pigment 254. The photosensitive resin composition according to item 1 of the patent application scope, wherein the photosensitive resin composition further includes at least one additive selected from the group consisting of malonic acid; 3-amino-1,2-propanediol; Coupling agents based on (meth) acrylic acid; leveling agents; fluorine-based surfactants; and radical polymerization initiators. A color filter manufactured by using the photosensitive resin composition as described in the first item of the patent application scope.